On a current mechanism in Ta2O5 thin films

Electrical conduction in the temperature range of 120–370 K has been studied in sandwiched structures of Al/Ta₂O₅/Si. The tantalum oxide films were prepared by evaporation of tantalum on a p-Si crystal substrate, followed by oxidation at a temperature of 600°C. The temperature-dependent current-voltage (I–V) characteristics are explained on the basis of a phonon-assisted tunnelling model. The same explanation is given for I–V data measured on Ta₂O₅ films by other investigators. From the comparison of experimental data with theory the density of states in the interface layer is derived and the electron-phonon interaction constant is assessed.      

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Synthesis and characterization of sol-gel derived Mn2+ doped In2S3 nanocrystallites embedded in a silica matrix

Mn²⁺ doped In₂S₃–SiO₂ nanocomposite thin films were synthesized by sol-gel technique. The films were annealed in air at different temperatures (473–623 K) and characterized by optical, microstructural and electron spin resonance (ESR) study. Optical transmittance study revealed the manifestation of quantum size effect while ESR indicated the presence of manganese in indium sulphide as dispersed dopant rather than manganese cluster.     

Electrochromic materials from the visible to the infrared region: an example WO<Subscript>3</Subscript>

Herein, the example of the most typical electrochromic material, namely WO₃, is used to illustrate the potential of electrochromic materials for controlling infrared reflectance and hence, emissivity. Playing with various growth parameters, contrast in reflectance between the inserted H _xWO₃ and deinserted WO₃ states as high as 73% in mid-wavelength band (MW, 3–5 μm) was achieved for 320 nm WO₃ films. The latter electrochromic materials were radio frequency sputtered on Au substrate at ambient temperature in 6 Pa of chamber pressure. In comparison, for long wavelength band (LW, 8–12 μm), the contrast in reflectance did not exceed 30%. The origins of the various electrochromic behaviours are correlated to the film structure, morphology and composition, indicating better properties for porous, nonstoichiometric films. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

氢气引入对宽光谱Mg和Ga共掺杂ZnO透明导电薄膜的特性影响

为适应宽光谱高效率硅基薄膜太阳电池的应用需求,本文尝试采用直流磁控溅射技术在553 K衬底温度下生长氢化Mg和Ga共掺杂ZnO(HMGZO)透明导电氧化物(TCO)薄膜.通过对薄膜微观结构、表面形貌、电学以及光学性能的测试和分析,详细地研究了氢气(H2)流量(0—16.0 sccm)对HMGZO薄膜结晶特性及光电性能的影响.实验结果表明:生长获得的HMGZO薄膜均为六角纤锌矿结构的多晶薄膜,择优取向为(002)晶面生长方向.薄膜的生长速率随着氢气流量的增加呈现逐渐减小趋势,主要归因于溅射产额的减小.适当的氢气引入会引起晶粒尺寸的增加.随着氢气流量由0增加至4.0 sccm,ZnO薄膜电阻率从177?·cm急剧减小至7.2×10-3?·cm,主要是由于H施主的引入显著地增加了载流子浓度;然而进一步增加氢气流量(4.0—16.0 sccm)造成电阻率的轻微增加,主要归因于载流子浓度的减小以及过多氢杂质引入造成杂质散射的增加.所有生长获得的HMGZO薄膜平均光学透过率在波长λ～320—1100 nm范围内可达87%以上.由于Mg的作用及Burstein-Moss效应的影响造成了带隙展宽,带隙变化范围～3.49—3.70 eV,其中最大光学带隙Eg可达～3.70 eV.     

Nickel nanostructured materials from liquid phase photodeposition

Liquid Phase Photo-Deposition (LPPD) technique has been used to obtain both colloidal particles and thin films of metallic and chloride nickel from solutions of only precursor Ni(acac)₂ (acac=2,4-pentandionato). Metallic nickel was obtained from ethanol solutions by direct nickel(II) photoreduction at 254 nm and by acetone sensitised reaction at 300 nm. In this latter process the rate was higher than in the first one. NiCl₂ was formed from CCl₄ solution by a solvent-initiated reaction. TEM analysis, performed on colloidal particles of nickel, showed that their dimensions are in the range 2–4 nm. The films did not present carbon contamination and were characterized by AFM, XPS and GIXRD. Metallic films consisted of particles of 20–40 nm that are the result of the aggregation of smaller crystallites (4–5 nm). Larger agglomerations (around 200 nm) have been observed for NiCl₂ films.     

Electrosynthesis of TiO2 oxide film on ITO substrate and electrochemical comparative study of the oxide with its hydrated gel

Thin TiO₂ films obtained by cathodic electrosynthesis from an acidic aqueous bath containing TiOSO₄, H₂O₂ and KNO₃ on conductive glass indium tin oxide have been physically and electrochemically characterised. Secondary ion mass spectroscopy profile of the crystallised gel after heat treatment at 400 °C shows the presence of TiO₂ with traces of TiO and oxygen. X-ray patterns confirm the presence of anatase nanocrystallites for the annealed film and an amorphous structure for the non-annealed gel. Scattering electron microscopy surface micrographies reveal an opened porous nanostructure of the deposits. Cyclic voltammetry and impedance spectroscopic measurements reveal the different behaviour of the films obtained before and after the annealing, showing an important electrical activity of the non-annealed films. The dependence of capacitance values with potential in the anodic domain of depletion is obviously remarked from impedance plots for both gel and crystal forms of the film, which confirmed the fact that films obtained in this way have n-type properties. The potential of flat band equals −0.6 V/Ag/AgCl in pH range of 6.5 has been estimated according to Mott–Shottky curves for the crystallised oxide; meanwhile, the Mott–Shottky curve for the hydrated gel was nonlinear.     

Electro-optical response due to mixed conduction electrodes, compared to ferroelectric ones, in asymmetric nematic liquid crystal cells

The usual liquid crystal cells show an electro-optical response symmetric to the applied voltage. On the contrary, when mixed conduction films such as tungsten trioxide or vanadium pentoxide are inserted on one side of the cell, the electro-optical response is asymmetric with respect to the applied voltage. Depending on the structural phase of the inserted film the electro-optical response is in phase (transmission ON during the anodic polarization on metal oxide electrode, transmission OFF during the cathodic one) or in opposition of phase (reverse combination). The first case has been explained by the formation of a double charge layer at the interface metal oxide–liquid crystal, because of migration of protons contained in the oxide films. The other case has been found after high-temperature treatments of metal oxides deposited on glass–ITO substrates, and it appears quite similar to the response collected by using films of ferroelectric materials such as lead zirconium titanate (PZT). This fact suggests a possible interpretation in terms of dielectric response, when the mixed conduction films undergo high-temperature treatments. A comparative study of films of WO₃, V₂O₅, and PZT is carried out in this work as a function of the annealing temperature. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Structural and electrical characterisation of strontium zirconate proton conductor co-sputter deposited coatings

SrZr_1−x Y _x O₃ coatings were co-sputtered from metallic Zr–Y (84–16 at.%) and Sr targets in the presence of a reactive argon–oxygen gas mixture. The structural and chemical features of the film have been assessed by X-ray diffraction and scanning electron microscopy. The electrical properties have been investigated for different substrates by Complex Impedance Spectroscopy as a function of crystalline state, temperature and atmosphere. The as-deposited coatings are amorphous and crystallise after annealing at 673 K for 2 h under air. The stabilisation of the perovskite structure is a function of the nominal composition. The films are dense and present a good adhesion on different substrates. Crystallisation and mechanical stresses are detected by alternating current (AC) impedance spectroscopy. Significant ionic conductivity in the 473–823 K temperature range is evidenced in air. Two different conduction regimes in the presence of steam are attributed to a modification of the charge carrier nature. In spite of low conductivity values (σ ~10⁻⁶ S.cm⁻¹ at 881 K), the activation energies are in agreement with that of Y-doped strontium zirconate ceramics (~0.7 eV in air).     

Ionic conduction in plasticized PVC/PAN blend polymer electrolytes

Blended polymer electrolytes with poly(vinyl chloride) (PVC)–poly(acrylonitrile) (PAN) were prepared with different plasticizer concentrations and constant lithium perchlorate (LiClO₄) ratio by the solution-casting technique. The structure and complexation of the prepared films were studied by X-ray diffraction and Fourier transform infrared spectroscopy. The effect of the plasticizer on the ionic conduction in these electrolytes was investigated using alternating current impedance measurement and discussed. The temperature-dependant ionic conductivity was carried out in the range 302–373 K. The prepared films were also examined by thermogravimetry/differential thermal analysis to determine their thermal stability.     

Synthesis and electrical properties of Ln<Subscript>2</Subscript>CuO<Subscript>4+</Subscript><Subscript><Emphasis Type="Italic">δ</Emphasis></Subscript> (Ln: Nd or La) mixed conductor sputter deposited coatings

Nd₂CuO₄ and La₂CuO₄ are potential candidates as cathode material for intermediate temperature-solid oxide fuel cells. Nd–Cu and La–Cu oxides were co-sputtered on rotating substrates from metallic La, Nd and Cu targets in the presence of a reactive argon–oxygen gas mixture. Structural and chemical features of these films have been determined by X-ray diffraction and energy-dispersive spectroscopy. Their electrical resistivity was measured using the four-point probe method. As-deposited Nd–Cu based coatings are amorphous and, after annealing, crystallise in K₂NiF_{4+ δ} -type structure for Nd/Cu atomic ratio of 2, with more or less Nd₂O₃ or CuO, depending on whether Nd or Cu is in excess, respectively. As-deposited La–Cu based coatings are also amorphous and crystallise in La₂CuO₄ for La/Cu >2 or in LaCuO_3±δ perovskite-type structure when Cu is in excess. The electrical measurements show a clear relation between resistivity and structure of the coatings. After annealing, crystallised neodymium-based coatings show higher resistivity than lanthanum-based ones. Finally, LaCuO_3±δ exhibit higher resistivity than La₂CuO₄. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Structural,morphological and photoluminescence characteristics of sol-gel derived nano phase CeO<Subscript>2</Subscript> films deposited using citric acid

Homogenous nano structured CeO₂ films have been prepared by a sol-gel process using different mole ratios of citric acid as additive. XPS studies clearly illustrate an increase in Ce³⁺ proportion upon the use of higher citric acid content for the deposition of films. The crystallite sizes in the films lie in the nanorange. Photoluminescence emission in the films is attributed to various defects resulting from crystallization. Lowest transparency, high Ce³⁺ content and optimum sized crystallites in CeO₂ (1:1.5) films have led to its highest PL characteristics. Ce³⁺ chemical state is the major contributor to the PL activity of these films. The SEM micrographs show a reduced level of CeO₂ agglomeration in the films deposited using higher citric acid contents. A comparison of different properties of CeO₂ films deposited using citric acid and CeO₂–TiO₂ films has also been made.      

Defect formation in thin films of the semiconductor compound Cu(In,Ga)Se2 when bombarded by protons

We have used low-temperature (4.2–78 K) photoluminescence to study defect formation processes in Cu(In,Ga)Se₂ films when bombarded by protons with energy 380 keV. We have observed formation of luminescence centers with deep levels at ∼410 meV and 470 meV. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 828–830, November–December, 2006.     

Characterization and antibacterial functions of Ag–TiO<Subscript>2</Subscript> and W–TiO<Subscript>2</Subscript> nanostructured thin films prepared by sol-gel/laser-induced technique

A novel sol-gel/laser-induced technique (SGLIT) has been developed to form nanocrystalline titanium dioxide (TiO₂) based thin films with an improved antibacterial performance. TiO₂ precursor films loaded with W⁺⁶ and Ag⁺² ions (W–TiO₂, Ag–TiO₂) were prepared separately by sol-gel method and spin-coated on microscopic glass slides. As-dried films were subjected to KrF excimer laser pulses at optimized parameters to generate mesoporous anatase and rutile phases at room temperature. The anatase phase was obtained after irradiation with 10 laser pulses only at 75–85 mJ/cm² fluence in W–TiO₂ films. However, higher number of laser pulses and higher W⁺⁶ content favored the formation of rutile. Whereas Ag–TiO₂ films exhibited anatase up to 200 laser pulses at the same fluence. The films were characterized by using XRD, FEG-SEM, TEM and UV-Vis spectrophotometer to investigate the crystallographic structure, phase transformation, surface morphology, film thickness and the optical properties. A crystallite size of approximately 20 nm was achieved from the anatase prepared by SGLIT. The films exhibited an enhanced antibacterial function against E-Coli cells under the UV excitation.     

Correlation of thickness and magnetization in LCMO film

High quality thin films of La_0.67Ca_0.33MnO₃ (LCMO) of different thickness were grown on LAO substrates by pulsed laser deposition (KrF, λ = 278 nm). The AFM images suggest a twodimensional step-growth. DC magnetization measurements of the films in a field of 500 Oe show that the magnetic ordering temperature is the same for all the films in both FC and ZFC conditions and is the same as that for the bulk. However, a difference is seen between the FC and ZFC magnetization of the films. There seems to be a systematic in this difference with respect to the thickness of the film, with the difference decreasing with thickness. We suggest that the difference in the magnetization under FC and ZFC conditions may be due to strain-induced anisotropy arising from the lattice mismatch between the substrate and the film or due to the shape anisotropy due to epitaxial growth Article presented at the International Symposium on Advances in Superconductivity and Magnetism: Materials, Mechanisms and Devices, ASMM2D-2001, 25–28 September 2001, Mangalore, India.     

Low-macroscopic field emission from nanocrystalline Al doped SnO<Subscript>2</Subscript> thin films synthesized by sol–gel technique

We have observed low-macroscopic field electron emission from wide bandgap nanocrystalline Al doped SnO₂ thin films deposited on glass substrates. The emission properties have been studied for different anode-sample spacings and for different Al concentrations in the films. The turn-on field and approximate work function were calculated and we have tried to explain the emission mechanism from this. The turn-on field was found to vary in the range 5.6–7.5 V/μm for a variation of anode sample spacing from 80–120 μm. The turn-on field was also found to vary from 4.6–5.68 V/μm for a fixed anode-sample separation of 80 μm with a variation of Al concentration in the films 8.16–2.31%. The Al concentrations in the films have been measured by energy dispersive X-ray analysis. Optical transmittance measurement of the films showed a high transparency with a direct bandgap ∼3.98 eV. Due to the wide bandgap, the electron affinity of the film decreased. This, along with the nanocrystalline nature of the films, enhanced the field emission properties. PACS 81.20.Fw; 61.10.-i; 79.70.+q     

Investigation of CuInSe2 films by the method of photoacoustic spectroscopy

We investigated the photoacoustic spectra of polycrystalline thin CuInSe₂ films obtained by the method of pulsed laser evaporation onto glass substrates at 100–450°C. The spectra were taken near the fundamental optical absorption edge using a high-resolution spectrometer and microphone-type sensor. We show the relation between the photoacoustic spectrum and the structural properties of films. The interference effect observed is discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 583–586, July–August, 1999.     

The influence of lithium excess in the target on the properties and compositions of Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>2</Subscript>O<Subscript>4−<Emphasis Type="Italic">δ</Emphasis></Subscript> thin films prepared by PLD

Li–Mn–O thin films were deposited by pulsed laser deposition (PLD) onto stainless steel substrates using targets containing different concentrations of added Li₂O. The influence of the target composition on the stoichiometry of the resulting thin films, the surface morphology and the electrochemical properties was studied. The application of the target with added 7.5 mol% Li₂O results in an almost ideal lithium content, while all films were still oxygen deficient. The thin films were applied as electrodes in Li//Li_1+x Mn₂O_4−δ cells (i.e. model cells for a rechargeable Li-ion battery) and characterized by cyclic voltammetry and galvanostatic charge/discharge experiments. The electrochemical measurements of the thin films confirmed that the thin films can serve as good model systems and that they show a sufficient cyclability.     

Pseudo-capacitive properties of LiCoO<Subscript>2</Subscript>/AC electrochemical capacitor in various aqueous electrolytes

LiCoO₂ particles were synthesized by a sol-gel process. X-ray diffraction analysis reveals that the prepared sample is a single phase with layered structure. A hybrid electrochemical capacitor was fabricated with LiCoO₂ as a positive electrode and activated carbon (AC) as a negative electrode in various aqueous electrolytes. Pseudo-capacitive properties of the LiCoO₂/AC electrochemical capacitor were determined by cyclic voltammetry, charge–discharge test, and electrochemical impedance measurement. The charge storage mechanism of the LiCoO₂-positive electrode in aqueous electrolyte was discussed, too. The results showed that the potential range, scan rate, species of aqueous electrolyte, and current density had great effect on capacitive properties of the hybrid capacitor. In the potential range of 0–1.4 V, it delivered a discharge specific capacitance of 45.9 Fg^–1 (based on the active mass of the two electrodes) at a current density of 100 mAg^–1 in 1 molL^–1 Li₂SO₄ aqueous electrolyte. The specific capacitance remained 41.7 Fg^–1 after 600 cycles.     

Structural,optical and electrical properties of post annealed Mg doped ZnO films for optoelectronics applications

Mg _x Zn_1-x O films with 0.15 mole composition of Magnesium were successfully deposited by the spin coating sol–gel method. Zinc acetate dihydrate and Magnesium acetate were used as starting precursors to prepare the solution in ethanol solvent. The MgZnO films were deposited on microscopic glass substrates and post annealed at three different temperatures. X-ray Diffractometer (XRD), Scanning Electron Microscopy (SEM) and UV–VIS Spectrophotometer were used to characterize the deposited films for studying structural and optical properties. Energy dispersive analysis by X-ray (EDAX) was used to determine incorporation of Mg content in ZnO films. XRD spectrum reveals that, the deposited Mg doped ZnO films were polycrystalline in nature. The intensity of c-axis in the XRD spectrum goes on decreasing as Mg composition slightly increasing corresponding to increase in annealing temperature. EDAX spectra clearly showed the incorporation of Mg into the ZnO films. Semiconductor characterization system was used for the I–V characterization of MgZnO films. I–V characteristics show decrease in current as increase in the biased voltage. Optical band gap of MgZnO films was found to be increased from 3.2 to 3.38 eV as estimated from the absorption coefficients.